The mechanisms by which organisms control the stability of amorphous calcium carbonate (ACC) are yet not fully understood. Previous studies have shown that the intrinsic properties of ACC and its environment are critical in determining ACC stability. Here, the question, what is the effect of bulk incorporation versus surface adsorption of additives on the stability of synthetic ACC, is addressed. Using a wide range of in situ characterization techniques, it is shown that surface adsorption of poly(Aspartic acid) (pAsp) has a much larger stabilization effect than bulk incorporation of pAsp and only 1.5% pAsp could dramatically increase the crystallization temperature from 141 to 350 °C. On the contrary, surface adsorption of PO43− ions and OH− ions does not effectively stabilize ACC. However, bulk incorporation of these ions could significantly improve the ACC stability. It is concluded that the stabilization mechanism of pAsp is entirely different from that of PO43− and OH− ions: while pAsp is effectively inhibiting calcite nucleation at the surface of ACC particle, the latter acts to modify the ion mobility and delay crystal propagation. Thus, new insights on controlling the stability and crystallization processes of metastable amorphous materials are provided.

No abstract

The crystallization pathways of amorphous calcium carbonate (ACC) have attracted tremendous interests because of the importance of ACC in biomineralization. Here, by using poly(Aspartic acid) with a chain length of...

Calcite mesocrystals were proposed and have been widely reported to form in the presence of polymer additives via oriented assembly of nanoparticles. However, the formation mechanism and the role of polymer additives remain elusive. Here, inspired by the biomineralization process of sea urchin spine comprising magnesium calcite mesocrystals, we show that calcite mesocrystals could also be obtained via attachment of amorphous calcium carbonate (ACC) nanoparticles in the presence of inorganic zinc ions. Moreover, we demonstrate that zinc ions can induce the formation of temporarily stabilized amorphous nanoparticles of less than 20 nm at a significantly lower calcium carbonate concentration as compared to pure solution, which is energetically beneficial for the attachment and occlusion during calcite growth. The cation-mediated particle attachment crystallization significantly improves our understanding of mesocrystal formation mechanisms in biomineralization and offers new opportunities to bioprocess inspired inorganic ions regulated materials fabrication.

Enameloid is the most highly mineralized tissue of shark tooth with excellent mechanical properties, which consists of fluorapatite (FAP) crystallites in the form of intricate hierarchical arrangement. However, the crystallization...